Thioglycolic amides



.- Patented pe rl,- 194a:

THIOGLYGOLIC AMIDES Arnold Weissberger, Charles J. Kibler, and Richard V. Young, Rochester, N. Y alalgn'ora to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No. Original Serial N0. 539.780.

application June 10, 1944. Divided and this tion March 15, 1945, Serial No. 583,002

5 Claims. (01. zoo-45 s) This invention relates to photographic coloriorming or coupling compounds and particularly to coupler compounds which are non-diflusing when incorporated in sensitive emulsion layers.

This application is a division of our application, Serial No. 539,780, filed June 10, 1944.

In Peterson U. 8; Patent 2,298,306, granted September 22, 1942, and U. 8. Patent 2,353,754, granted July 18, 1944, there are described couplers which contain a heterocyclic ring and a free 10 imino or mercapto group which is capable of forming a metallic salt inphotographic emulsions. These compounds are quite non-.diflusing in photographic emulsions but combine with the development product of primary aromatic amino reacting with the development product of the developing agent to. form a dye image.

developing agents to form colored images in the well-known manner. Upon fixing, the metallic ,atom attached to the imino or mercapto group is removed and the unused coupler may be washed from the layer.

- previously used are not, however, readily washed 1 from the emulsion layer after fixing and tend to decompose and discolor the final image.

It is, therefore, an .object of the present invention to provide a new class of coupler compounds ,single position in the coupler molecule. By re irom which insoluble metallic salts may be formed in the emulsion layer. A further object is to provide coupler compounds which are readily soluble in the fixing bath and which may be readily removedfrom the emulsion layer. Other so derivative of a coupler havin the following g group may be substituted by certain groups withwhere R and B'=hydrogen or alkyl groups, and '40 This group occurs in the phenolic andl naptholic M=a heavy metal. These insoluble couplers are produced iro coupling compounds of the following probable formula:

- These couplers are formed by introducing the thioglycolic amide portion of the molecule into Some of the couplers so compounds which react with primary aromatic T any well-known type of coupler compound, such as those described in Fisher U. 8. Patent 1,055,155,

Mannes and Godowsky U. 5. Patents 2,039,730, 2,108,602, and 2,113,330 or Marines, Godowsky, and Peterson U. 3. Patents 2.115594 and 2,126,337. It is to be understood that when we rei'er'to introducing the thioglycolic amide por- .tion into non-coupler compounds, we do not mean that the final compound is necessarily formed by simple substitution starting with these two materials. The final compound may be formed by any suitable reaction which results in a compound having a thioglycolic amide portion as described above and a coupling portion or portions containing at least one group capable of The "coupler" portion of the molecule indicated in the general formulas above contains the iunctional or reactive group common to coupler amino developing agents to form colored images. This functional or reactive group is usually a reactive methylene or reactive ethenol group and may occur at various positions or more than a active methylene, we mean a CH: group which is reactive in the coupling process. This group is usually present between two negative centers as, for example, in the groups: a

in a ring system or chain compound. One or both of the hydrogen atoms of the methylene coupler compounds which are reactive in the ortho or para portion with respect to the position of the hydroxyl group. a

The compounds which we propose to use may have the following structure:

- 3 where R; R and X are mula above, and the phenol nucleus may contain other substituents, as long as it is unsubstituted the same as in the foror contains a replaceable substltuent, such as halogen, in theposition para to the hydroxyl group; or the following structure:

ONES o omen 2-hydroxy-thioglycolic anilidc CHhO-NHCOCHiSH 2-hydroxy-4-methyl-thioglyoolic anilidc on cmoG-mzco omen 2-hydroxy i-methoxy-thioglyeolic anilido 0 v CHr-QNHCOCILSH l v z-hydroxy-l-methylchlorothioglycolic anilide Cl on CHy-QNHQOCESH 2-11ydi-oxy-3,5-dichloro4-methyithioglycolic anilide CH NHCObH-SCOCH:

2-(atylmercaptopropionamido)- 4,6-d1chloro-5-methylphenol CH: OH:

on NHCO sH 2-hydroxy-4-methyl-5-chloro- (a-dimethylthioglycolic anilide) O0 ocmc ONHQNHC oonisn w-Benzoylacetamino-p-thioglycolic anilide Molekulverbindungen (1922),'pages 60, 125i,- 153 cocmcoNn noocmsn u-Banzoylacotamino-m-thloglyoollc anllido n O-cocnic oNnONHcocmsooom u-Bcnzoylaoetamlno-p-aoetyl-thioglycollc anillde u-Bonzoylacetamino-m-ace t'ylthloglyoolic anllido (18) C 0 CHiCN 00 (misc 0 CH: p-Acetylthloglycolylamino-wcyanoaoetophanone u mo o-woman 4 1-phenyl-3 (thioglycolylamino)-5-pymolonc is cmcocmcoNn-O-Nacoomsoocm Acetoaeetylaminopaoetylthioglyoolic anlllde The coupler compounds used according to our invention are generally incorporated in the emulsion layer by first forming a solution of the sodium or other soluble salt of the coupler and then incorporated in a silver halide emulsion whereupon part of the silver or the silver halide replaces the sodium to form the silver salt of the coupler. Other heavy metal salts such as gold, nickel, mercury, cadmium or tin may be formed before the coupler is incorporated in the silver halide emulsion. Silver salts are preferred, however, since a silver salt is ordinarily used in the production of sensitive layers and common silver salts, such as silver chloride or silver bromide are suitable for the purpose of our invention. Other silver salts which may be used are silver ferricyanide, silver ortho phosphate, silver arsenate, silver oxalate,

the acetyl derivatives of the thioglycolic amides,

it is possible that the reaction with the silver re- A sults in the formation of a complex rather than a pure salt. The formation of such additional complexes is suggested by P. Pfeifl'er, Organlsche and 289.

The non-diffusing metal salts made according to our invention may be incorporated in single or multi-layer gelatin emulsion coatings or in layers of other colloidal materials such as cellu- I lose esters or neutral or synthetic resins, and mixtures of the couplers may be used in a single layer.

The couplers which we propose to use are made in general by condensing thioglycolic acid or Compound is prepared as follows:

In a 1-liter round-bottomed flask is placed 163 grams (0.715 molelof purified 2-amino-4,6-dichloro-5-methylphenol hydrochloride. To the hydrochloride is added 210 grams (2.38 mole) of thioglycolic acid and 109.5 grams (0.845 mole) (100 cc.) of quinoline. The mixture is stirred 2 well and the flask is immersed in the steam bath and covered with a towel. The heating is con-. tinued for 5 hours with shaking at intervals. The reaction mixture is a brown liquid with some undissolved hydrochloride. The mixture is cooled to about 35 and then stirred into 1 liter of water; at first a liquid forms which rapidly changes to, a mass of soft lumps. The crude anilide is 'filtered, washed with 1 liter of water and sucked stirred solution. The temperature rises quickly and a precipitate forms. This precipitate was stirred occasionally over a period of about an almost dry on the filter. The product is then dried in a'vacuumdesiccator over the weekend. Yield of crude product is 145 grams (76.0%) M. P.

Purification 3 The 145 grams of crude grey anilide is dissolved in 1200 cc. of boiling benzene, filtered and the filtrate is chilled rapidly to about 10. The anilide crystallizes in small colorless crystals which are filtered and washed on the filter with 150 cc. of cold (10) benzene. The product is then sucked dry on the filter. Recovery is 116 grams (80%) M. P. 138-139.

The 116 grams of anilide is recrystallized a second time from 1200 cc. of boiled benzene, filtered and then chilled to 10. The crystals are filtered and washed with150 cc. of cold benzene. Recovery is 109 grams (91.5%) M. P. 1385-1395". The third and final crystallization is carried out by dissolving the 109 grams of anilide in 1300 cc. of boiled chloroform, filtering and chilling to 0. The product crystallizes in small crystals which are filtered off and then washed with 200 cc. of ice-cold chloroform. The product is sucked dry on the filter. The anilide is placed in a vacuum desiccator overnight. Recovery is 87 grams (80%) M. P. 139-140". Yield of purifled product is 46%.

Compounds 1, 2, 3, 4, 8 and 1d are in a similar manner, using the corresponding amine in place of 2-amino-4,6-dichloro-5-methylphenol hydrochloride.

Compound 7 is prepared by a method similar to that used in the preparation of Compound 5, using the corresponding amine and 2-mercaptoisobutyric acid (Billmann, Ann. 348, 129) instead of thioglycolic acid. The free base of the amine is employed, rather than the hydrochloride, and no quinoline is necessary. a

Compound 13 is prepared'as follows:

' crnc oe-cmc 001 NH oocmcN hour. The materials were poured into. a beaker and 300 cc. of .water was added. The precipitate was thoroughly washed with water and then with alcohol. Twenty-seven grams of productwas recrystallized from 1500 cc. of alcohol. The product was decolorized with Darco. The material was recrystallized a second time, the solution standing overnight in the refrigerator before filterlng. Yield: 20 grams of recrystallized mate- 0 rial (61% of the theoretical) M. P. 195.

Acetylthioglycolic acid crncoc1+HscH=cooH- cmcoscmcoon+nc1 In a socc. 3-necked flask fitted with a condenser, stirrer, and dropping funnel was placed 139 cc. (2 moles) thioglycolic acid, Then 175 cc. (2.5 moles) of acetyl chloride was added through the dropping funnel to the stirred mixmm at such a rate as to cause rapid, but not too vigorous, evolution of HCl. The mixture warms spontaneously. It was transferred to a 500-cc. modified C'laisen flask with a10-inch column and distilled under reduced pressure. A

5 forerun of about 50 grams B. ripen-100, was

collected. ,Then the mixture was cooled slightly and the distillation continued using a high-vacuum. The fraction, 3. P.a.s 115-118..w8$ collected as acetylthioglycolic acid. It amounted to (See Ber. 46, 1913, 2105).

Acetulthioglucolyl chloride cnlhoscmcoln+soonv cmcoscmcoc1+so=+nc1 A 500-cc. 3-necked round-bottomed fiaslr fitted with a thermometer, stirrer, outlet tube, nd an additional funnel is charged with 102 grams (0.75 mole) of acetyl thioglycolic acid. The flask is immersed in a. water bath maintained at about 20 as 93 cc. (1.27 moles) of thionyl chloride is added dropwise to the stirred solution at such a rate as to cause evolution of HCl and S0: and to keep the temperature of the reaction mixture at 25,-30. After about 30% of the thionyl chloride is added, the vigor of the reaction subsides considerably so that the remainder may be added prepared rapidly. The mixture is stirred overnight at room temperature. The excess thionyl chloride is removed at reduced pressure; heating the fiask gently by means or a water bath which is gradually warmed from 25-65. Then 50 cc. of dry benzene .is added;. this is removed at reduced pressure. After repeating this process once more, the water bath is gradually warmed to as the last traces of benzene and thionyl chloride are removed. Finally the product is distilled through a short column using two water pumps to take care or decomposition at the initial part of the distillation. The fraction boiling at 98-101 under 16-18 mm. is collected as pure acetylthioglycolyl chloride. The yieldjs 73 grams (64%). (Ber.46, 2105.) I

Compounds 11 and 12 are prepared by condensing p-(benzoylacetamino) -aniline or mcm.cocrnc0,c,m m

benzoylacetamino)=-aniline with acetylthioslycolyl chloride in a manner similar to that usedin the preparation of compound 13. m-(Benzoylacetamino) -aniline is prepared as follows, and p- (benzoylacetamino) -aniline is similarly prepared, using ethyl acetate as a solvent instead of alcohol:

m-(Benzoylacetammm-amlme o-Benzoyl-m-nitroacetanilide 'mmcocmcoun N: canon Forty-five grams of ethyl benzoylacetate, in an open beaker, is heated on an oil bath to 170-180".

Then 22 grams of m-nitroaniline is added in small increments during 15 minutes, always al-- lowing time between each addition for the alcohol to beevolved and for the temperature of the solution to rise above 165. Heating is continued for another 15 minutes, and, after the solution is allowed to cool somewhat, 75 cc. of benzene is added. The bright yellow crystalline product is filtered and washed with ether. The yield is 25 grams of w-benzoyl-ln-nitroacetanilide; M, P. 136-137".

Compound 10 is prepared from compound 12 as follows:

D-BBILZOIIIGOCtlZmiRO-M-th10gl1/C0li0 anilide NaOH CeHgCOCHzCONH NHCOCHISCOCHI Cc sCOGHsCONH NHCOCHISH To a. suspension of 1.85 gram (0.005 mole) of benzoyl-acetamino-m-acetylthioglycolic anilide in cc. of alcohol is added cc. of 5 per cent sodium hydroxide (0.0125 mole), and the mixture is stirred until solution is effected. The solution is diluted to 25 cc., filtered and let stand 10 minutes. The alkaline solution is kept at room temperature (25 C.) throughout. The product separates as a sum when the solution is acidified with 10 cc. of 10 per cent acetic acid. After washing several times with water, the gum slowly crystallizes. There is obtained 1.25 gram of wbenzoylacetamino-m-thioglycolic anilide melting at 148-149".

Compound 9 is similarly prepared from 'compound 11.

Compound 15 is prepared by condensing p- (acetoacetamino) aniline with acetylthioglycolyl chloride in a manner similar to that used in the preparation oi Compound 13.

Compound 6 is prepared as follows:

2-(e-Bromopropionamtdo)-4,6-dichloro-5 methulphenol on A 01 Manor 15 Br COCHBr 2NaOAc on m 01 NHCOCHBr OH H; NaGl NaBr 2 HOAc To a well-stirred suspension of 22.8 grams (0.1 mole) of 2-amino-4,6-dichloro-5-methylphenol hydrochloride and 17.5 grams (0.2 mole) of anhydrous sodium acetate in 200 cc. of glacial acetic acid was added 21.6 grams (0.1 mole) of m-blOIllO- propionyl bromide. The mixture was stirred at 50 for two hours, and theri flooded with water. The oil was extracted with ether, and the ether layer washed, dried and concentrated. The residue was recrystallized from benzene,'M. P. 144-146.

2- (a-acetylrnercaptopropionamido) -4,6- dichl0ro-5-meth1 lphenol 40 c NHCOCHBr +Kscocn.

on e 4-) Cl uncocnscocm K H8 Br 1 To a solution of potassium thioacetate prepared from 0.4 gram of thioacetic acid and 0.23 gram of potassium hydroxide in 15 cc. of ethyl alcohol was added 1.6 grams of 2-(a-bromopropionamido) -4,6-dichloro-5-methy1phenol. The clear solution warmed to 35 and potassium bromide 0 separated. After standing overnight, water. was added and the solid collected on a. filter. It was recrystallized from diluted alcohol; M. P. 132-133".

The following examples, which are illustrative 5 only,,indlcate a method of forming a. multi-layer photographic element, using the couplers of our invention:

A cyan coupler solution is'prepared by dissolving 6.9 grams (0.03) of 2-hydroxy-4-methy1- 5-chloro-thioglycolic anilide in 120 cc. of 2% sodium hydroxide. A very fine silver chloride emulsion is prepared by a well-known procedure containing 6.4 grams (0.045 mole) of silver chloride in 880 cc. of a 2.3% gel solution. The cyan coupler solution is added with rapid stirring to this very fine grain silver chloride emulsion. This forms a silver salt of the cyan coupler in very fine dispersion. This coupler dispersion may then be mixed with an equal volume of a higher speed red-sensitized emulsion and coated on a support, spreading 45 grams of coupler per thousand square feet.

A magenta coupler solution is prepared by dissolving 5.5 grams (0.02 mole) of p-acetylthioglycolylamino-w-cyanoacetophenone in 72 cc. of 2% sodium hydroxide. A very fine grain silver chloride emulsion is prepared by a well-known method containing 4.3 grams (0.03 mole) of silver chloride in 928 cc. of a 1.1% gel solution. The magenta coupler solution is added with rapid stirring to this very fine grain silver chloride emulsion. This forms a silver salt of the magenta coupler in very fine dispersion. This coupler dispersion may then be mixed with one-half the volume of a higher speed green-sensitized emulsion and coated on the red-sensitized cyan layer spreading 60 grams of coupler per thousand square feet.

A yellow filter layer is coated over the red and green-sensitive layers to protect them from the blue light to which they are inherently sensitive. This filter layer may consist of a very fine dispersion of silver prepared by the Carey-Lea Dextrin method. It should be coated so it has a density of 2.0 to light of wave length 420 m The yellow coupler is prepared by dissolving 7.4 grams (0.02 mole) of w-benzoylacetamlnop-acetylthioglycolic anilide in 80 cc. of 2% sodium hydroxide. A very fine silver chloride emulsion is prepared by a well-known procedure containing 4.3 grams (0.03 mole) of silver chloride in 920 cc. of 1.1% gel solution. The yellow coupler solution is added with rapid stirring to this very fine grain silver chloride emulsion. This forms a silver salt of the yellow coupler in very flne dispersion. This coupler dispersion may then be mixed with one-half the volume of a higher speed unsensitized emulsion and coated over the filter layer. This layer of yellow coupler is the top and final coat of the multi-layer coating. The layer should be spread at about 120 grams per thousand square feet.

The emulsion layers coated in this way produce respectively cyan, magenta and yellow images upon development with a primary aromatic amino developing agent such as diethyl-p-phenylenediamine. The element may be exposed and deor on opaque supports, such as paper or pigmerited cellulose esters.

The modification and examples included herein are illustrative only. and it will be understood that our invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A compound having the probable formula:

R"NH-OOCSX where R" is selected from the class consisting of 2-hydroxy phenyl radicals and acylacetanilido radicals, R and R are selected from the class consisting of hydrogen and alkyl groups, and X is selected from the class consisting of hydrogen and acyl groups.

2. A compound having the probable formula: R\ n' rw-nn-c o-o-sx where R" is a Z-hydroxy phenyl radical and R and R are selected from the class consisting'of hydrogen and alkyl groups, and X is selected from the class consisting of hydrogen and acetyl groups.

3. A compound having the probable formula:

. n n' O-oocmoomrONnco-c-sx n-mroocmscocm so where R. is a z-hydroxy phenyl radical.

veloped directly to form a negative colored imase or a positive image may be obtained by first developing in an ordinary black-and-white developer followed y color development of the residual silver halide.

The emulsions containing our coupler compounds are developed with any suitable primary where x is selected from the class consisting of aromatic amino developing agent, such as the go Patent solutions described in Peterson U. 8.

5. A compound having the probable formula:

. NHCOOHsBX hydrogen and 'acetyl groups, and Y is an acyl sroup.

mom wmssnnnann. cnaanns J. mm. momma v. YOUNG. 

